CN115702219A - Photocurable ink composition for inkjet printing - Google Patents
Photocurable ink composition for inkjet printing Download PDFInfo
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- CN115702219A CN115702219A CN202180041232.XA CN202180041232A CN115702219A CN 115702219 A CN115702219 A CN 115702219A CN 202180041232 A CN202180041232 A CN 202180041232A CN 115702219 A CN115702219 A CN 115702219A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The present invention addresses the problem of providing a photocurable ink composition for inkjet printing, which, on the premise of having a viscosity suitable for ejection, is excellent in all of curability, adhesion after curing (non-tackiness), adhesion to various resin substrates, bending resistance, rub resistance, water resistance, ethanol resistance, and banding. As a solution, a photocurable ink composition for inkjet printing is provided, which is characterized by satisfying all the following conditions A to F: a: a total content of 1 or more compounds selected from the group consisting of vinylmethyloxazolidinone, N-dimethylacrylamide, benzyl acrylate, and N-vinylcaprolactam of 30.0% by mass or more in the photocurable inkjet printing ink composition; b: a total content of 1 or more compounds selected from a monofunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms and a polyfunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms, in the photocurable inkjet printing ink composition, of 15.0% by mass or more; c: a content of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide of 3.5% by mass or more in the photocurable inkjet printing ink composition; d: a total content of the ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and the bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide in the photocurable inkjet printing ink composition is 6.0 to 12.0% by mass, and the ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide is 0.3 to 1.5 in terms of a mass ratio; e: the content of the amine-modified oligomer is 0.5 to 15.0 mass% in the photocurable inkjet printing ink composition; f: and (5) color materials.
Description
Technical Field
The present invention relates to a photocurable ink composition for inkjet printing suitable for printing on a sheet or the like whose printing surface is made of a resin such as paper, a vinyl chloride polymer, or an ethylene-vinyl acetate copolymer, and a printed matter obtained using the photocurable ink composition.
Background
As described in patent document 1, a photocurable inkjet ink composition containing 8 parts by mass of TPO-L and 1 part by mass of Irgacure819, and further containing tricyclodecane dimethanol diacrylate is known.
As described in patent document 2, a photocurable inkjet ink composition containing 6 parts by mass of TPO-L and 1 part by mass of Irgacure819, and further containing N-vinylcaprolactam, isobornyl acrylate, and isodecyl acrylate is known.
As described in patent document 3, there are known an ink composition for inkjet containing 2 parts by mass of TPO-L and 6 parts by mass of Irgacure819, further containing N-vinylcaprolactam and isobornyl acrylate, and a photocurable ink composition for inkjet containing 4 parts by mass of TPO-L and 2 parts by mass of Irgacure819, further containing a polymerizable compound.
As described in patent document 4, a photocurable inkjet ink composition containing 4.1 to 13.5 parts by weight of TPO-L, 1.4 to 6.4 parts by weight of Irgacure819, and further containing N-vinylcaprolactam and isobornyl acrylate is known.
The ink jet system has the following features: the range of materials that can be used as the printing substrate is wide, and printing can be easily performed on sheets of paper, polymers, metals, other hard or soft arbitrary materials. Particularly, a sign advertisement installed outdoors needs to be lightweight, excellent in strength and durability, strong in rain-proofing property, and inexpensive, and therefore, it is very advantageous that it can be easily printed on a polymer sheet having these characteristics.
In addition, recently, an ink jet printer that prints an ultra-wide width of 2,000mm or more has been marketed, and it is possible to print a large-sized printed matter or the like that has been processed by pasting so far at a time, and thus it is possible to manufacture a billboard more easily.
In general, as a polymer sheet for billboard advertising, a waterproof tarpaulin is generally used. The waterproof tarpaulin is a composite sheet in which a core material is polyester or polyamide and a vinyl polymer such as polyvinyl chloride or ethylene-vinyl acetate copolymer is laminated on the surface and the back.
However, as shown in patent documents 1 to 4, although a photocurable inkjet ink composition containing TPO-L and Irgacure819 is known, no ink is obtained that is excellent in all of curability, adhesiveness, rub resistance, water resistance, ethanol resistance, and banding when printed on various resin substrates. Further, there has not been known an ink in which the solubility of the photopolymerization initiator in the photocurable inkjet ink composition is taken into consideration, and the composition of the entire composition is taken into consideration.
Further, the photocurable ink composition for inkjet printing cannot satisfy these high requirements.
Patent literature
Patent document 1: japanese patent laid-open publication No. 2019-137735
Patent document 2: japanese patent laid-open publication No. 2019-151714
Patent document 3: japanese patent laid-open No. 2015-030796
Patent document 4: japanese patent laid-open publication No. 2012-201815
Disclosure of Invention
The present invention addresses the problem of providing a photocurable ink composition for inkjet printing, which is excellent in all of curability, adhesion after curing (non-adhesion), adhesion to various resin substrates, rub resistance, water resistance, ethanol resistance, and banding, on the premise of having a viscosity suitable for ejection.
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by employing a specific composition, and have completed the present invention.
That is, the present invention is as follows.
1. A photocurable inkjet printing ink composition characterized by satisfying all of the following conditions A to F:
a: a total content of 1 or more compounds selected from the group consisting of vinylmethyloxazolidinone, N-dimethylacrylamide, benzyl acrylate, and N-vinylcaprolactam of 30.0% by mass or more in the photocurable inkjet printing ink composition;
b: a total content of 1 or more compounds selected from a monofunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms and a polyfunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms, in the photocurable inkjet printing ink composition, of 15.0% by mass or more;
c: a content of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide of 3.5% by mass or more in the photocurable inkjet printing ink composition;
d: a total content of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide in the photocurable inkjet printing ink composition is 6.0 to 12.0% by mass, and the ratio by mass of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide is 0.3 to 1.5;
e: the content of the amine-modified oligomer is 0.5 to 15.0 mass% in the photocurable inkjet printing ink composition;
f: and (6) color materials.
2. The photocurable ink composition for inkjet printing according to claim 1, wherein 16.0% by mass or more of benzyl acrylate is contained as the compound expressed by the condition A.
3. The photocurable inkjet printing ink composition according to claim 1 or 2, wherein the following condition G is satisfied:
g: contains a pigment dispersant having a tertiary amino or nitrogen-containing heterocyclic structure.
The photocurable inkjet printing ink composition of the present invention contains a coloring material, has a low viscosity, is excellent in solubility of a photopolymerization initiator, has no tackiness on the surface of a cured coating film, is excellent in adhesion to various substrates, rubbing resistance, water resistance and ethanol resistance, and can exhibit an effect of preventing a banding phenomenon of the coating film.
Detailed Description
The photocurable inkjet printing ink composition of the present invention satisfies the above conditions a to F, and the following description is given in order.
< Condition A >
The condition a is a total content of 1 or more compounds selected from the group consisting of vinyl methyl oxazolidinone (5-methyl-3-vinyl oxazolidin-2-one) (hereinafter sometimes referred to as "VMOX"), N-dimethylacrylamide, benzyl acrylate, and N-vinyl caprolactam (hereinafter sometimes referred to as "VCAP"), and is 30.0 mass% or more in the photocurable inkjet printing ink composition. If the amount is less than 30.0% by mass, it becomes difficult to dissolve the photopolymerization initiator in the photocurable inkjet printing ink composition, and it becomes difficult to function as an ink composition.
These compounds are liquids having low viscosity at normal temperature, and exhibit excellent ink jet printing suitability. Further, it can dissolve or disperse other components in the photocurable inkjet printing ink composition. And has excellent solubility in a photopolymerization initiator as shown below. Further, since the cured film is also excellent in safety to the human body, the workability is good, and the cured film exhibits low odor, high curability, and high water resistance.
The total content of the 1 or more compounds selected from the above is preferably 32.0% by mass or more, and more preferably 34.0% by mass or more in the photocurable inkjet printing ink composition. In addition, the photocurable inkjet printing ink composition is preferably 50.0% by mass or less, and more preferably 40.0% by mass or less.
Further, benzyl acrylate is preferably contained in the photocurable ink composition for inkjet printing, and in this case, the content thereof in the photocurable ink composition for inkjet printing is preferably 16.0% by mass or more, more preferably 18.0% by mass or more, further preferably 20.0% by mass or more, and most preferably 25.0% by mass or more. Further, it is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, further preferably 35.0% by mass or less, and most preferably 30.0% by mass or less.
Vinyl methyl oxazolidinone, N-dimethylacrylamide and N-vinylcaprolactam are preferably used together with benzyl acrylate, and also preferably contain benzyl acrylate and any 1 of these compounds, or benzyl acrylate and vinyl methyl oxazolidinone and N, N-dimethylacrylamide.
More preferably, the total content of 1 member selected from the group consisting of vinylmethyloxazolidinone, N-dimethylacrylamide and N-vinylcaprolactam is less than the content of benzyl acrylate.
< Condition B >
The condition B is a total content of 1 or more compounds selected from a monofunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms and a polyfunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms, and is 15.0% by mass or more in the photocurable inkjet printing ink composition. The saturated hydrocarbon group may be any of an alkyl group having 6 or more carbon atoms, an alkylene group, and a group having a cyclic structure.
In such a saturated hydrocarbon group having 6 or more carbon atoms, the number of carbon atoms is preferably 20 or less, more preferably 15 or less, and still more preferably 12 or less.
The monofunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms and the polyfunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms are preferably 18.0% by mass or more in total in the photocurable inkjet printing ink composition. In addition, the photocurable inkjet printing ink composition is preferably 30.0% by mass or less, and more preferably 25.0% by mass or less.
(monofunctional monomer having C6 or higher saturated hydrocarbon group)
As the monofunctional monomer having a saturated hydrocarbon group having 6 or more carbon atoms, isooctyl (meth) acrylate, tridecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isotetradecyl (meth) acrylate, isobornyl (meth) acrylate, and the like can be used. Among them, isobornyl acrylate is preferred.
(polyfunctional monomer containing C6 or more saturated hydrocarbon group)
As the polyfunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, or the like can be used. Among them, hexanediol diacrylate is preferable.
< Condition C >
The condition C is that the content of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Irgacure Omnirad 819) is 3.5% by mass or more in the photocurable ink composition for inkjet printing. And is preferably 4.0% by mass or more, more preferably 4.5% by mass or more, and further preferably 5.0% by mass or more. Further, it is preferably 8.5% by mass or less, and more preferably 6.5% by mass or less.
When the content of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is less than 3.5% by mass, the surface curability, adhesion and abrasion resistance of the coating film may be deteriorated.
< Condition D >
The condition D is that the combination of the contents of 2 kinds of photopolymerization initiators is defined, the total content of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide is 6.0 to 12.0% by mass in the photocurable inkjet printing ink composition, and the ratio by mass of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide is 0.3 to 1.5.
When the total content of the ethoxy (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and the bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide is less than 6.0% by mass in the photocurable ink composition for inkjet printing, the stringiness is deteriorated, and the surface curability, adhesiveness, adhesion, abrasion resistance and water resistance may also be deteriorated. If it exceeds 12.0 mass%, the solubility of the photopolymerization initiator is poor and the banding property is also poor.
The total content of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide is preferably 6.5% by mass or more, more preferably 7.0% by mass or more, further preferably 7.5% by mass or more, and most preferably 8.0% by mass or more in the photocurable ink composition for inkjet printing. Further, it is preferably 11.0% by mass or less, more preferably 10.5% by mass or less, further preferably 10.0% by mass or less, and most preferably 9.5% by mass or less.
If the ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide ratio is less than 0.3 by mass, the surface curability, adhesion to a partial substrate, abrasion resistance, water resistance and stringiness of the coating film are deteriorated, and if it exceeds 1.5, the adhesion, abrasion resistance and stringiness are deteriorated, and further, the surface curability and water resistance may be deteriorated.
Ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, preferably 0.40 or more, more preferably 0.50 or more. Further, it is preferably 1.00 or less, more preferably 0.80 or less.
< Condition E >
Under condition E, the content of the amine-modified oligomer in the photocurable inkjet printing ink composition is 0.5 to 15.0% by mass.
The amine-modified oligomer includes acrylated amine compounds such as oligomers of acrylated amine compounds having 2 photopolymerizable functional groups and 2 amino groups in the molecule, namely CN371, CN373, CN383, and CN386 (manufactured by Sartomer corporation).
If the content of the amine-modified oligomer in the photocurable inkjet printing ink composition is less than 0.5% by mass, the surface curability, the adhesiveness, and the rub resistance are deteriorated, and if it exceeds 15.0% by mass, the viscosity of the photocurable inkjet printing ink composition becomes too high, which may deteriorate the balance of the properties of the photocurable inkjet printing ink composition.
The content of the oligomer having an amino group in the photocurable inkjet printing ink composition is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, still more preferably 3.0% by mass or more, and most preferably 4.0% by mass or more. Further, it is preferably 12.0% by mass or less, more preferably 10.0% by mass or less, further preferably 8.0% by mass or less, and most preferably 7.0% by mass or less.
< other photopolymerizable monomers >
The photocurable inkjet printing ink composition of the present invention may contain, in addition to the above-mentioned monomers, other monofunctional or polyfunctional photopolymerizable monomers. However, other photopolymerizable monomers are used within a range not to impair the effects of the present invention.
Among such photopolymerizable monomers, examples of monofunctional photopolymerizable monomers include: monofunctional (meth) acrylates such as benzyl (meth) acrylate, butyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, caprolactone (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, and EO (ethylene oxide) -modified succinic acid (meth) acrylate.
In addition, there may be mentioned: acryloyl morpholine, acrylonitrile, acrylamide, diethylacrylamide, styrene, (meth) acrylic acid, and the like.
Such a monofunctional photopolymerizable monomer may not be contained, and when contained, it is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, and still more preferably 15.0% by mass or more in the photocurable inkjet printing ink composition. In addition, the photocurable inkjet printing ink composition preferably contains 40.0% by mass or less, more preferably 30.0% by mass or less, and still more preferably 28.0% by mass or less.
The polyfunctional photopolymerizable monomer is a compound having a plurality of carbon-carbon unsaturated bonds in the molecule, and the following compounds can be used, for example.
Examples thereof include: (poly) alkylene glycol di (meth) acrylates such as ethyleneoxyethoxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc.; dimethylol tricyclodecane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polytetramethylene glycol diacrylate, trimethylolpropane tri (meth) acrylate and ethylene oxide modifications thereof, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and ethylene oxide modifications thereof, dipentaerythritol penta (meth) acrylate and ethylene oxide modifications thereof, dipentaerythritol hexa (meth) acrylate and ethylene oxide modifications thereof, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, pentaerythritol ethoxy tetraacrylate, caprolactam modified dipentaerythritol hexaacrylate, ethoxylated bisphenol a diacrylate, alkoxylated tetrahydrofurfuryl acrylate, and the like.
Such a polyfunctional photopolymerizable compound as the other photopolymerizable monomer is not necessarily required to be contained, but when contained, the content thereof is 1.0 to 10.0% by mass in the photocurable inkjet printing ink composition.
The photocurable inkjet printing ink composition of the present invention may not contain an acrylic resin, and may be contained within a range not impairing the effects of the present invention. Examples of such acrylic resins include polymers and copolymers thereof composed of (meth) acrylic acid esters soluble in organic solvents. Examples of the (meth) acrylate include: alkyl (meth) acrylates such as ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypentyl (meth) acrylate.
Examples thereof include BR-60 (Tg: 75 ℃ C.), BR-64 (Tg: 55 ℃ C.), BR-75 (Tg: 90 ℃ C.), BR-77 (Tg: 80 ℃ C.), BR-83 (Tg: 105 ℃ C.), BR-87 (Tg: 105 ℃ C.), BR-88 (Tg: 105 ℃ C.), BR-90 (Tg: 65 ℃ C.), BR-93 (Tg: 50 ℃ C.), BR-95 (Tg: 80 ℃ C.), BR-105 (Tg: 50 ℃ C.), BR-106 (Tg: 50 ℃ C.), BR-107 (Tg: 50 ℃ C.), BR-108 (Tg: 90 ℃ C.), BR-113 (Tg: 75 ℃ C.), BR-115 (Tg: 50 ℃ C.), and BR-116 (Tg: 50 ℃ C.) manufactured by Mitsubishi chemical corporation.
When the acrylic resin is contained, the content of the acrylic resin is preferably 1.0 to 5.0% by mass, more preferably 1.5 to 4.0% by mass, and even more preferably 2.0 to 3.0% by mass, based on the total amount of the photocurable inkjet printing ink composition.
As the resin other than the acrylic resin, for example, a vinyl chloride-based resin, a vinyl chloride-vinyl acetate-based resin, an ethylene-vinyl acetate-based resin, a styrene-acrylic resin, a styrene-maleic resin, a rosin-based resin, a rosin ester-based resin, a petroleum resin, a coumarone-based resin, a terpineol-based resin, a phenol resin, a ketone resin, a polyurethane resin, a melamine resin, a urea resin, an epoxy-based resin, a cellulose-based resin, a xylene resin, an alkyd resin, an aliphatic hydrocarbon resin, a butyral resin, a maleic acid resin, a fumaric acid resin, or the like may be used in combination within a range in which the performance of the photocurable inkjet printing ink composition of the present invention is not deteriorated.
< Condition F >
The coloring material contained in the photocurable inkjet printing ink composition of the present invention is preferably selected from known organic coloring pigments and inorganic coloring pigments conventionally used in photocurable inkjet printing ink compositions. The coloring material is a coloring pigment other than titanium oxide, or a coloring pigment other than a white pigment.
Specific examples of the organic coloring pigment include: specific examples of the organic pigments include azo-based, azomethine-based, polyazo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, indigo-based, thioindigo-based, quinophthalone-based, benzimidazolone-based, isoindoline-based (isoindololine), isoindolinone-based (Isoindolinone), pyrrolopyrrole-dione-based, and dioxazine-based pigments, which are represented by color indexes and include: pigment black 7, pigment blue 15, 15: 1. 15: 3. 15: 4. 15: 6. 60, pigment green 7, 36, pigment red 9, 48, 49, 52, 53, 57, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, pigment orange 36, 43, 51, 55, 59, 61, 71, 74, etc.
The content of the organic coloring pigment in the ink composition of the present invention is preferably 1.0 to 10.0% by mass in the photocurable inkjet printing ink composition, depending on the degree of color spreading desired.
(carbon Black)
As the inorganic coloring pigment, carbon black conventionally used in ink jet is used, and the smaller the average primary particle diameter is, the more the abrasion resistance and gloss of the obtained colored image tend to be improved, so that the average primary particle diameter is preferably 15 to 40nm, more preferably 20 to 30nm.
The average primary particle diameter of carbon black is a value determined in the following manner. First, a dispersion in which carbon black was sufficiently diluted and dispersed in chloroform was prepared to such a degree that when images of aggregates of carbon black were taken by a Transmission Electron Microscope (TEM), the images of the aggregates on the photographs did not coincide with each other. Then, the film was developed on a collodion film-attached net and dried, and a TEM photograph was taken in this state (magnification after magnification was 3 ten thousand times). Then, the TEM photograph was read by a scanner, the image signal was digitized, and the digitized image signal was recorded in a computer, and the area of each aggregate was obtained by image analysis. Further, the average area of the primary particles was obtained from the area of each aggregated body and the number of aggregated primary particles, and the diameter of a circle having the same area as the average area was defined as the arithmetic average primary particle diameter. Finally, the average primary particle size is determined by arithmetically averaging the average primary particle sizes of all or a specific number of the aggregates.
When carbon black is contained in the present invention, the content of carbon black is 1.0 to 12.0% by mass, preferably 2.0 to 6.0% by mass, based on the whole photocurable inkjet printing ink composition. If the content is less than 1.0 mass%, the density of the obtained image may be low, and if it exceeds 12.0 mass%, the ejection stability of the ink jet ink composition may be lowered.
Further, the specific surface area of the carbon black to be used is preferably 80 to 150m 2 Per g, more preferably 100 to 130m 2 (ii) in terms of/g. Within this range, the color image is particularly preferable in terms of abrasion resistance, solid printing integrity, and the prevention of mottling.
The carbon black to be used is preferably acidic carbon black, and more preferably has a pH of 2.5 to 4.0.
The specific surface area of the carbon black is a nitrogen adsorption specific surface area measured according to JIS K6217, and the pH is a pH value measured according to JIS K6221.
Examples of such carbon black include: mitsubishi carbon black MA7, MA77, MA8, MA11, MA100, MA220, etc.
(other inorganic coloring pigments)
Examples of other inorganic coloring pigments include: titanium oxide, zinc white, zinc oxide, lithopone, iron oxide, silicon dioxide, kaolin, montmorillonite, talc, barium sulfate, calcium carbonate, silica, cadmium red, iron oxide red, molybdenum red, chromium red, molybdenum orange, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chromium green, cobalt green, titanium cobalt green, cobalt chromium green, ultramarine blue, prussian blue, cobalt blue, azure blue, manganese violet, cobalt violet, mica, and the like.
These pigments may be used in an amount of 0.5 to 10.0% by mass, more preferably 2.0 to 7.0% by mass, based on the total amount of the photocurable inkjet printing ink composition, as long as the effects of the present invention are not impaired. When the amount of the pigment used is less than 0.5% by mass, the coloring ability tends to be insufficient, while when the amount is more than 10.0% by mass, the viscosity tends to be increased and the fluidity of the ink tends to be lowered.
In addition, a white pigment such as titanium oxide can be used together with other coloring pigments, but the effect of the present invention is not impaired when used. Further, a white pigment such as titanium oxide or titanium oxide may not be contained.
(pigment dispersant)
Examples of the pigment dispersant that may be contained when the pigment is contained in the photocurable inkjet printing ink composition of the present invention include ionic or nonionic surfactants, and anionic, cationic or nonionic polymer compounds.
Among them, preferred are polymeric compounds, for example, carbodiimide compounds described in Japanese patent laid-open publication No. 2004-083872, international publication No. WO2003/076527, and International publication No. WO2004/000950, ajisEPR PB821 and 822 (manufactured by Ajinomoto Kogyo Co., ltd.) (both acid value and amine value are 10 to 20 mgKOH/g), SOLSPERSE56000 (manufactured by LUBRIZOL Co., ltd.), SOLSPERSE39000 (manufactured by LUBRIZOL Co., ltd.), DISPERBYK (manufactured by BYK JAPAN Co., ltd.), and the like. These pigment dispersants may be used in 1 kind or in a mixture of 2 or more kinds, and the amount thereof is 5 to 80% by mass, more preferably 10 to 60% by mass, based on the pigment.
Among them, a copolymer having a basic functional group with an amine value of 10 to 40mgKOH/g is preferable.
The pigment dispersant may be appropriately selected and used according to the type of pigment and the type of organic solvent used.
< Condition G >
Among the above pigment dispersants, a pigment dispersant having a tertiary amino group or a nitrogen-containing heterocyclic structure is particularly preferably contained.
As such pigment dispersants, it is preferable to use SOLSPERSE20000, SOLSPERSE32000, BYK-LP N6918, BYK-LP N21116, DISPERBYK161, DISPERBYK164, DISPERBYK167, DISPERBYK2164, BYKJET9150, BYKJET9151, efka PX4320, efka PX4701, efka PX4703, and the like.
(organic solvent)
The photocurable inkjet printing ink composition of the present invention may be a so-called solventless type in which all liquid components are cured through a curing reaction, or a solvent type in which a coating film after printing is dried to remove a solvent and then cured. However, water is not used as a solvent.
Hereinafter, the case where the photocurable inkjet printing ink composition of the present invention contains an organic solvent will be described.
Examples of the organic solvent that may be contained in the photocurable ink composition for inkjet printing according to the present invention include propylene carbonate, diethylene glycol dialkyl ether, and dipropylene glycol alkyl ether acetate.
As the diethylene glycol dialkyl ether, diethylene glycol ethyl methyl ether and/or diethylene glycol diethyl ether is preferably used, and further, other diethylene glycol dialkyl ethers may be used in combination.
The dipropylene glycol alkyl ether acetate is preferably an alkyl group having 6 or less carbon atoms, more preferably an alkyl group having 3 or less carbon atoms, and still more preferably an alkyl group having 2 or less carbon atoms.
In addition, in order to adjust the drying property and further improve the spot formation preventing property, an alkylene glycol derivative having a flash point of 50 to 150 ℃ may be used in combination with diethylene glycol dialkyl ether.
Examples of the alkylene glycol derivative having a flash point of 50 to 150 ℃ include: (poly) ethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether and tetraethylene glycol dimethyl ether, (poly) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tetrapropylene glycol diethyl ether and tetrapropylene glycol dimethyl ether, (poly) propylene glycol monoalkyl ethers such as propylene glycol monobutyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether, propylene glycol monoalkyl ether acetates, propylene glycol monobutyl ether acetates, dipropylene glycol monomethyl ether acetates, dipropylene glycol monoethyl ether acetates, and dipropylene glycol monobutyl ether acetates, (poly) propylene glycol monoalkyl ether monoalkyl esters such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, (poly) ethylene glycol monoalkyl ether monoesters such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether and the like, (poly) ethylene glycol monoalkyl ether monoalkyl esters such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate and the like, (poly) ethylene glycol diesters such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate and the like, (poly) ethylene glycol monoethyl ether monoesters such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate and the like, (poly) ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate and the like.
Among the alkylene glycol derivatives having a flash point of 50 to 150 ℃, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether are listed.
Further, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, etc., which do not have a flash point in the range of 50 to 150 ℃ may be used in combination within a range in which the flash point of the entire solvent is not largely changed.
(photopolymerization initiator)
As the photopolymerization initiator used in the present invention, 2 kinds of photopolymerization initiators used in conditions C and D can be used. Namely, ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: TPOL manufactured by Lambson) and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad819 manufactured by BASF).
Furthermore, it is necessary not to use (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide (trade name: TPO, manufactured by Lambson) in consideration of the workability of the photocurable ink composition for inkjet printing at the time of production or use.
(sensitizer)
Further, in order to promote the curability with respect to ultraviolet rays using a Light Emitting Diode (LED) as a light source, the following photosensitizers (compounds) may be used together with a polymerization initiator in the photocurable inkjet printing ink composition of the present invention: the photosensitive composition has a light absorption property mainly in an ultraviolet wavelength region of 400nm or more, and exhibits a sensitizing function of a curing reaction by light having a wavelength in this range.
Examples of such a sensitizer include anthracene sensitizers and thioxanthone sensitizers, and the thioxanthone sensitizers are preferred. These may be used alone or in combination of 2 or more.
Specifically, there may be mentioned: anthracene-based sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis (2-ethylhexyloxy) anthracene; thioxanthone sensitizers such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone and 4-isopropylthioxanthone. As typical examples of commercially available products, DBA and DEA (manufactured by Kawasaki chemical industry Co., ltd.) are exemplified as anthracene-based sensitizers, and DETX and ITX (manufactured by Lambson) are exemplified as thioxanthone-based sensitizers.
The content of the sensitizer is preferably 0 to 8.0% by mass based on the total mass of the photopolymerizable components. Even if the amount exceeds 8.0 mass%, the effect cannot be improved, and the addition amount is excessively increased, which is not preferable.
In addition, when a thioxanthone sensitizer is used as the sensitizer, the content of the thioxanthone sensitizer is preferably determined appropriately for each color because the photocurable inkjet printing ink composition tends to become yellow and to have a more yellowish hue than a color (original hue) based on a pigment or the like.
Specifically, it is preferable that the white ink composition and the clear ink composition which are susceptible to a change in color tone do not contain a thioxanthone compound as a sensitizer. Further, in the magenta ink composition and the cyan ink composition, since there is a problem in hue change, it is preferably used in a range where hue is not problematic. Further, since the black ink composition and the yellow ink composition do not affect the hue even if they are discolored and are different in photopolymerization from other colors, it is preferable to use a thioxanthone-based compound in combination as a sensitizer.
(other Components)
Further, in the photocurable inkjet printing ink composition of the present invention, various additives such as a surfactant, a plasticizer, a polymerization inhibitor, a surface conditioner, an ultraviolet inhibitor, a photostabilizer, an antioxidant and the like may be used as required.
(viscosity of ink composition for photocurable inkjet printing)
The viscosity of the photocurable inkjet printing ink composition of the present invention at 25 ℃ is preferably 30.0mPa · s or less, more preferably 20.0mPa · s or less, even more preferably 10.0mPa · s or less, and most preferably 8.0mPa · s or less. If it exceeds 30 mPas, the ink composition may be difficult to be discharged from the nozzle for ink jet printing.
The viscosity was measured at 25 ℃ and 20rpm using an E-type viscometer (trade name: RE 100L-type viscometer, manufactured by Toyobo industries Co., ltd.).
(production of Photocurable ink composition for inkjet printing)
Next, a method for producing the photocurable inkjet printing ink composition of the present invention using these materials will be described.
The photocurable inkjet printing ink composition of the present invention can be obtained, for example, by performing dispersion mixing using a dispersion machine such as a wet circulation Mill, a bead Mill, a ball Mill, a sand Mill, a vertical ball Mill (attritor), a roll Mill, a DCP Mill, a stirrer, a henschel mixer, a colloid Mill, an ultrasonic homogenizer, a high-pressure homogenizer (Micro fluidizer, nanomizer, ultizer, genus PY, deBEE2000, etc.), a Pearl Mill (Pearl Mill), etc., and adjusting the viscosity of the photocurable inkjet printing ink composition to 2 to 10mPa · s.
The total organic solvent content in the photocurable inkjet printing ink composition of the present invention is an amount obtained by subtracting the total amount of the solid components and other additives used as needed from the total amount of the ink composition, and the ink viscosity is preferably appropriately changed so as to fall within the above range.
The photocurable inkjet printing ink composition of the present invention obtained as described above can be used on a substrate having at least a surface layer made of paper, a vinyl chloride polymer, an ethylene-vinyl acetate copolymer, or other resin, using an inkjet printer.
(use)
The photocurable inkjet printing ink composition of the present invention can be used for known applications including paper substrates, and is particularly suitable for use in the case of a surface layer of a substrate which is required to have abrasion resistance and is made of a non-absorbent material. The non-absorbent material may be any material such as metal, resin, ceramic, etc., and among them, a surface layer using a resin as a base material is preferably used in terms of water resistance, etc., and a surface layer made of a vinyl chloride polymer, an ethylene-vinyl acetate copolymer, a vinyl chloride resin, polyethylene terephthalate, polycarbonate, etc. is preferably used as the resin. In addition, in terms of adhesion and the like, it is preferable to use a surface layer made of polyethylene terephthalate (PET), vinyl chloride resin, polycarbonate, tarpaulin, acrylic resin or the like as the resin.
Specifically, the method of printing and curing the photocurable inkjet printing ink composition of the present invention includes a method of discharging the photocurable inkjet printing ink composition of the present invention onto a substrate through an inkjet head, and then curing the coating film of the ink composition of the present invention discharged onto the substrate by light exposure.
For example, the ejection (printing of an image) onto a substrate can be performed by supplying the photocurable ink composition for inkjet printing of the present invention to a print head corresponding to a low viscosity of an inkjet recording printer and ejecting the ink composition from the print head so that the film thickness of a coating film on the substrate becomes, for example, 1 to 60 μm. The exposure to light and curing (curing of an image) can be performed by irradiating a coating film of the photocurable ink composition for inkjet printing of the present invention applied as an image on a substrate with light.
As a printing apparatus for inkjet recording system for printing the photocurable inkjet printing ink composition of the present invention, a conventionally used printing apparatus for inkjet recording system can be used. When a printing apparatus for continuous inkjet recording is used, the photocurable inkjet printing ink composition of the present invention is further added with a conductive agent to adjust the conductivity.
The light source used for curing the coating film includes ultraviolet rays (UV lamp), ultraviolet rays (light emitting diode (LED)), electron beams, visible rays, and the like, and from the environmental viewpoint, a Light Emitting Diode (LED) that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420nm is preferable.
The ultraviolet ray using a Light Emitting Diode (LED) as a light source means "light emitted from a light emitting diode that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420 nm".
Examples
The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. In addition, "%" and "parts" are indicated as "% by mass" and "parts by mass", respectively, unless otherwise specified.
The materials used in the following examples and comparative examples are as follows. The unit of the numerical values in the columns relating to the pigments, dispersants, resins, solvents and total in the tables is "mass%".
The photopolymerizable compound a in the table is a compound prepared in accordance with the condition a in the present invention, and similarly, the photopolymerizable compound B is a compound prepared in accordance with the condition B in the present invention.
(amine-modified oligomer)
CN371 (manufactured by Sartomer corporation)
(photopolymerizable Compound A)
VMOX: vinyl methyl oxazolidinone
(photopolymerization initiator)
TPOL: ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide
Omnirad 819: bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide
TPO:2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by Lambson)
(sensitizer)
DETX: diethylthioxanthone (manufactured by Lambson Co., ltd.)
(polymerization inhibitor)
And (5) UV-5: dioctyl maleate (manufactured by Kromachem Co., ltd.)
(surface conditioner)
BYK-315N: polyester-modified polymethylalkylsiloxane surfactant, solid content 25 mass%, solvent component: mixture of methoxypropyl acetate and phenoxyethanol at a mass ratio of 1/1 (BYK JAPAN Co., ltd.)
(color Material (pigment))
PB15: 4. pigment blue 15:4
PR122 pigment Red 122
PY155 pigment yellow 155
PBk7 carbon black
PO71 pigment orange 71
PG7 pigment green 7
PV23 pigment Violet 23
PR254 pigment Red 254
(pigment dispersant)
SOLSPERSE32000 (polyamine pigment dispersant, manufactured by LUBRIZOL Co., ltd.)
BYKJET9150 (pigment dispersant having a maleimide structure, 70% by mass solid content, manufactured by BYK JAPAN Co., ltd.)
(examples 1 to 11 and comparative examples 1 to 10)
Production of photocurable ink composition for inkjet printing
The materials were mixed with stirring in the formulation ratios (blending ratio of each material is mass%) shown in table 1 to obtain photocurable inkjet printing ink compositions of examples and comparative examples.
< evaluation method and evaluation Standard >
The evaluation substrates described in table 1 are shown below.
PET: lumirror manufactured by Dongli corporation
PC: ifpilon Sheet FE2000, manufactured by Mitsubishi gas chemical Co., ltd
PVC: PVC80, manufactured by Lindebco
(viscosity of ink composition)
The photocurable inkjet printing ink compositions obtained in examples and comparative examples were measured for viscosity using an E-type viscometer (trade name: RE 100L-type viscometer, manufactured by Toyobo industries Co., ltd.) at a temperature of 25 ℃ and a spindle rotation speed of 20 rpm.
(solubility of photopolymerization initiator)
The components except for the pigment and the pigment dispersant in the compositions of examples and comparative examples were stirred and mixed at room temperature by a dispersing machine, and the time until the photopolymerization initiator was dissolved was measured and evaluated according to the following evaluation standards.
Good: dissolving in less than 1 hr
And (delta): dissolving for 1-2 hours
X: does not dissolve in 2 hours
(surface curing)
The photocurable inkjet printing ink compositions obtained in examples and comparative examples were applied to the surface of a PET film using a bar coater No.4 to obtain coated articles. Then, the resultant was irradiated with light at 120 W.times.50 m/min using a conveyor type light irradiator (STM-250E-16 manufactured by Heraeus, ltd.; lamp: Z-8 lamp (metal halide type)),UV cumulative light quantity 75mJ/cm 2 (the cumulative amount of UV light was determined by measuring the amount of irradiation in the measurement ranges of 250-260nm, 280-320nm, 320-390nm and 395-445nm using UVIMAP (UM 365H-S) manufactured by EIT Co., ltd.) under irradiation conditions, the number of times the device was passed (number of passes) until the surface tackiness disappeared was evaluated.
(tackiness)
The photocurable ink composition for inkjet printing obtained in examples and comparative examples was applied to each surface of 2 PET films using a bar coater No.4, and irradiated with ultraviolet rays to obtain a cured coating film.
The cured coating films on the surfaces of the 2 PET films thus obtained were temporarily stacked on each other, and the degree of resistance when peeled off by hand after 30 seconds was evaluated according to the following evaluation criteria.
Good component: resistance-free
And (delta): has resistance but no peeling of the coating
X: the coating film has peeling
(Adhesivity)
The photocurable inkjet printing ink compositions obtained in examples and comparative examples were applied to the surfaces of various substrates (PET, PC, PVC) using a bar coater No.4, and irradiated with ultraviolet rays to obtain cured coating films.
Adhesion of the obtained coating film was evaluated by the following evaluation criteria \12475125258612512503 (registered trademark, cellotape).
Good: without flaking off
X: with flaking off
(Friction resistance)
The photocurable ink compositions for inkjet printing obtained in examples and comparative examples were applied to the surface of a PVC film using a bar coater No.6, and irradiated with ultraviolet rays to obtain a cured coating film.
The obtained coating film was rubbed with bleached cloth 100 times by a chemical shaking fastness tester at a speed of 60rpm under a load of 500g, and the peeling of the coating film and the color shift to the bleached cloth were evaluated according to the following evaluation criteria.
Good component: produce no color shift or produce a color shift of less than 5% of the area
And (delta): generating a color shift of 5% or more and less than 70% of the area
X: producing a color shift of more than 70% of the area
(Water resistance)
The photocurable ink composition for inkjet printing obtained in examples and comparative examples was applied to the surface of a PVC film using a bar coater No.6, and irradiated with ultraviolet rays to obtain a cured coating film.
The obtained coating film was rubbed with a bleached cloth containing 5 drops of water 100 times by a chemical shaking fastness tester at a speed of 30rpm under a load of 500g, and the peeling of the coating film and the color shift to the bleached cloth were evaluated according to the following evaluation criteria.
Good: no color shift or a color shift of less than 5% of the area
And (delta): generating a color shift of 5% or more and less than 70% of the area
X: produce a color shift of 70% or more in area
(ethanol resistance)
The photocurable ink composition for inkjet printing obtained in examples and comparative examples was applied to the surface of a PVC film using a bar coater No.6, and irradiated with ultraviolet rays to obtain a cured coating film.
The obtained coating film was rubbed with bleached cloth containing 5 drops of 70% ethanol aqueous solution at a speed of 30rpm under a load of 200g by a chemical shaking fastness tester for 10 times, and the peeling of the coating film and the color shift to the bleached cloth were evaluated according to the following evaluation criteria.
Good component: produce no color shift or produce a color shift of less than 30% of the area
And (delta): generate a color shift of 30% or more and less than 70% of the area
X: producing a color shift of more than 70% of the area
(banding property)
The gloss at an angle of 60 ℃ was measured on a coating film printed on a PVC film by a commercially available ink jet printer using a gloss meter (trade name: glossMeter VG7000, manufactured by Nippon Denshoku industries Co., ltd.) and evaluated according to the following evaluation criteria.
Good: measured value of 15.0 or more
And (delta): measured value of 10.0 or more and less than 15.0
X: measured value of less than 10.0
[ Table 1-1]
[ tables 1-2]
[ tables 1 to 3]
According to the present invention, that is, according to each of examples 1 to 11, the coloring pigment is contained, and the coloring pigment has an appropriate viscosity, and the polymerization initiator exhibits excellent solubility, surface curability, adhesiveness, adhesion to various substrates, compatibility, abrasion resistance, water resistance, ethanol resistance, and stringiness.
On the other hand, in comparative example 1 in which the condition a (the total amount of the photopolymerizable compound a is small) is not satisfied, the polymerization initiator is not dissolved, and in comparative example 2 in which the condition B (the total amount of the photopolymerizable compound B is small), the tackiness, the rubbing resistance, the water resistance, the ethanol resistance, and the banding are poor.
According to comparative example 3 in which TPO was used as a photopolymerization initiator, the surface curability was slightly inferior, and the adhesiveness and the stringiness were inferior. Even in comparative example 4 using Omnirad819 in combination with TPO, the result of poor banding was obtained.
According to comparative example 5 in which the ratio of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide in condition D was too high, the viscosity of the photocurable inkjet printing ink composition was high and the adhesiveness, rubbing resistance and banding were poor, whereas according to comparative example 6 in which the ratio was too low, the surface curability, adhesiveness, rubbing resistance and water resistance were poor.
According to comparative example 7 in which condition C was not satisfied (the content of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide was small) and the ratio of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide was higher in condition D than in comparative example 5, the surface curability, adhesiveness, friction resistance, water resistance and stringiness were poor.
According to comparative example 8 in which the total content of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide was excessive under condition D, the photocurable inkjet printing ink composition had a high viscosity and the polymerization initiator had poor solubility and stringiness. On the contrary, comparative example 9, in which the total content is too small, is inferior in surface curability, adhesiveness, adhesion to a polycarbonate substrate, abrasion resistance, water resistance and stringiness.
According to comparative example 10 which did not contain the amine-modified oligomer of condition E, the surface curability, adhesiveness and abrasion resistance were poor.
Claims (3)
1. A photocurable inkjet printing ink composition characterized by satisfying all of the following conditions A to F:
a: a total content of 1 or more compounds selected from the group consisting of vinylmethyloxazolidinone, N-dimethylacrylamide, benzyl acrylate, and N-vinylcaprolactam of 30.0% by mass or more in the photocurable inkjet printing ink composition;
b: a total content of 1 or more compounds selected from a monofunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms and a polyfunctional monomer containing a saturated hydrocarbon group having 6 or more carbon atoms, in the photocurable inkjet printing ink composition, is 15.0% by mass or more;
c: a content of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide of 3.5% by mass or more in the photocurable inkjet printing ink composition;
d: a total content of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide in the photocurable inkjet printing ink composition is 6.0 to 12.0% by mass, and the ratio by mass of ethoxy (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide/bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide is 0.3 to 1.5;
e: the content of the amine-modified oligomer is 0.5 to 15.0 mass% in the photocurable inkjet printing ink composition;
f: and (5) color materials.
2. The photocurable inkjet printing ink composition according to claim 1, wherein 16.0 mass% or more of benzyl acrylate is contained as the compound expressed by the condition A.
3. The photocurable inkjet printing ink composition according to claim 1 or 2, wherein the following condition G is satisfied:
g: contains a pigment dispersant having a tertiary amino or nitrogen-containing heterocyclic structure.
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| JP2021013631A JP7354505B2 (en) | 2020-06-24 | 2021-01-29 | Photocurable inkjet printing ink composition |
| JP2021-013631 | 2021-01-29 | ||
| PCT/JP2021/021295 WO2021261208A1 (en) | 2020-06-24 | 2021-06-04 | Ink composition for photocurable inkjet printing |
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| EP (1) | EP4173825A4 (en) |
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| WO2021261208A1 (en) | 2021-12-30 |
| CN115702219B (en) | 2023-05-16 |
| EP4173825A1 (en) | 2023-05-03 |
| US20230312953A1 (en) | 2023-10-05 |
| EP4173825A4 (en) | 2024-07-17 |
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